CN114053859B - Hydrogen sulfide remover and preparation method thereof - Google Patents
Hydrogen sulfide remover and preparation method thereof Download PDFInfo
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- CN114053859B CN114053859B CN202111360017.4A CN202111360017A CN114053859B CN 114053859 B CN114053859 B CN 114053859B CN 202111360017 A CN202111360017 A CN 202111360017A CN 114053859 B CN114053859 B CN 114053859B
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- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
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- C10L3/10—Working-up natural gas or synthetic natural gas
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Abstract
The invention relates to a hydrogen sulfide remover and a preparation method thereof. The hydrogen sulfide remover is chelating agent containing aminomethylene diphosphonic acid and Fe 3+ Is a chelate compound of (a). The preparation method of the hydrogen sulfide remover comprises the following steps of chelate preparation: chelating agent containing aminomethylene diphosphonic acid and Fe containing 3+ The chelate compound is obtained as the hydrogen sulfide remover. The hydrogen sulfide remover of the invention contains a plurality of phosphate groups, and the phosphate groups and Fe 3+ Is very strong, even in a strongly acidic environment, fe 3+ The hydrogen sulfide is not easy to fall off, so that the efficiency of removing the hydrogen sulfide is high and stable when the hydrogen sulfide removing agent is used for removing the hydrogen sulfide.
Description
Technical Field
The invention relates to the field of hydrogen sulfide removal, in particular to a hydrogen sulfide remover and a preparation method thereof.
Background
The natural gas is a green clean energy, and the natural gas is used for replacing petroleum, so that the pollution problem of sulfur dioxide, dust and the like to the environment caused by petroleum can be effectively solved.
However, since the produced natural gas contains hydrogen sulfide gas, on the one hand, corrosion is caused to equipment and pipelines during the production and storage and transportation processes, and on the other hand, the natural gas is used as fuel to pollute the environment.
Therefore, the method for removing the hydrogen sulfide gas in the natural gas has great environmental protection and economic value.
At present, the hydrogen sulfide gas is removed mainly by adopting two types of wet method and dry method, and in actual industrial production, the dry method is widely applied in consideration of factors such as precision, energy consumption, cost and the like. The basic principle of dry desulfurization is to utilize gas-solid phase contact reaction, and make the solid hydrogen sulfide remover adsorb hydrogen sulfide gas or make the hydrogen sulfide gas and hydrogen sulfide undergo the chemical reaction so as to make the hydrogen sulfide gas be converted into solid sulfur or sulfide.
Common dry hydrogen sulfide removal agents include porous material hydrogen sulfide removal agents and metal oxide hydrogen sulfide removal agents. Wherein the porous material hydrogen sulfide remover is generally formed by loading metal salt (such as Fe salt and the like) with desulfurization performance on a carrier (such as active carbon, molecular sieve and the like) with developed pore structure through an impregnation method. And the metal oxide hydrogen sulfide remover mainly comprises ferric oxide and zinc oxide. Among these hydrogen sulfide removal agents, the supported iron-based hydrogen sulfide removal agent is widely used because of simple preparation and low cost.
However, the existing load type iron-based hydrogen sulfide remover has the problems of poor stability and low hydrogen sulfide removing efficiency in the use process.
For example, chinese patent document CN112717931a discloses an iron-based composite hydrogen sulfide remover, a preparation method thereof and application thereof in removing hydrogen sulfide, and the specific method is as follows: preparing ferric salt solution with a certain concentration, adding a certain proportion of carbon nano tubes, stirring to prepare mixed solution, adding a precipitator at a certain temperature to regulate the pH value of the solution to 3-11, forming suspension, aging, carrying out suction filtration after the aging is finished, collecting precipitate, and washing with deionized water to prepare the iron-based composite hydrogen sulfide remover. The method mainly utilizes the chemical bond interaction of Fe-O-C formed between the carbon nano tube and hydrated ferric oxide, thereby realizing the loading of ferric salt on the carbon nano tube. However, the bond energy between C-O bonds in Fe-O-C chemical bonds formed between the carbon nanotubes and the hydrated ferric oxide is low, the carbon nanotubes are easy to break under the acidic condition, and the treatment process of the hydrogen sulfide is strong in acidity, so that the hydrated ferric oxide gradually falls off on the surface of the carbon nanotubes, and the efficiency of removing the hydrogen sulfide is reduced.
Based on this, it is highly desirable to provide a hydrogen sulfide removal agent which is highly efficient and stable in hydrogen sulfide removal.
Disclosure of Invention
The invention provides a hydrogen sulfide remover and a preparation method thereof, which solve the problems of low removal efficiency and instability of the hydrogen sulfide remover in the prior art.
According to an aspect of the present invention, there is provided a hydrogen sulfide removing agent which is a chelating agent containing aminomethylene diphosphonic acid and Fe 3+ Is a chelate compound of (a).
According to the hydrogen sulfide removing agent of the present invention, the chelating agent containing aminomethylene diphosphonic acid is a cross-linked product of aminomethylene diphosphonic acid and a base having an amino group at the end.
According to the hydrogen sulfide removing agent of the present invention, the substrate having an amino group at the end is a conjugate of a hydroxyl group-containing substrate and an amino group-containing silane coupling agent.
According to the hydrogen sulfide removing agent of the present invention, the hydroxyl group-containing matrix is hydroxyl group-containing silica.
According to the hydrogen sulfide removing agent disclosed by the invention, the silicon dioxide containing hydroxyl is mesoporous silicon dioxide.
According to another aspect of the present invention, there is provided a method for preparing a hydrogen sulfide remover, comprising the steps of: chelating agent containing aminomethylene diphosphonic acid and Fe containing 3+ The chelate compound is obtained to be used as a hydrogen sulfide remover;
preferably, the chelating agent containing aminomethylene diphosphonic acid and the Fe-containing agent 3+ The mass ratio of the compounds is 1:7.5-1:25.
The preparation method comprises the preparation steps of the chelating agent containing the aminomethylene diphosphonic acid:
the amino methylene diphosphonic acid is crosslinked with a matrix with the tail end comprising amino groups through a crosslinking agent to obtain the chelating agent containing the amino methylene diphosphonic acid;
preferably, the mass-volume ratio of the aminomethylene diphosphonic acid to the matrix of which the tail end comprises amino groups is 1:40g/ml to 1:60g/ml.
The preparation method comprises the preparation steps of a matrix with the tail end comprising amino groups:
and coupling the hydroxyl-containing matrix with an amino-containing silane coupling agent to obtain the matrix with the amino-containing end.
Preferably, the mass ratio of the hydroxyl-containing matrix to the amino-containing silane coupling agent is 1:1-1:5.
The preparation method comprises the following steps of: and treating the matrix by an alkaline solution to obtain the hydroxyl-containing matrix.
According to the preparation method of the invention, the matrix is mesoporous silica.
Compared with the prior art, the beneficial effects generated by utilizing the technical scheme of the invention are as follows:
the hydrogen sulfide removing agent according to the present invention is based on one hand on the phosphate group and Fe in the chelating agent containing aminomethylene diphosphonic acid 3+ Is very strong, even in a strongly acidic environment, fe 3+ Is not easy to fall off, so when the catalyst is used for removing hydrogen sulfide, fe 3+ The hydrogen sulfide is not easy to fall off, so that the efficiency of removing the hydrogen sulfide is kept stable; on the other hand, since the chelating agent adopts the aminomethylenediphosphonic acid, the chelating agent contains rich amino groups and phosphate groups, and can chelate a large amount of Fe 3+ Thus improving the efficiency of removing the hydrogen sulfide; in yet another aspect, the hydrogen sulfide removal agent of the present invention may be regenerated by oxygen (i.e., fe by oxygen) 2+ Oxidation to Fe 3+ ) The hydrogen sulfide removing agent is reused.
According to the preparation method of the hydrogen sulfide remover, the hydrogen sulfide remover can be prepared.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below by means of examples, and it is obvious that the described examples are only some of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
According to an aspect of the present invention, there is provided a hydrogen sulfide remover which is a chelating agent containing aminomethylene diphosphonic acid and Fe 3+ Is a chelate compound of (a).
According to the hydrogen sulfide removing agent, on one hand, the chelating agent containing the aminomethylene diphosphonic acid can ionize a large amount of hydrogen ions in water and form a large amount of coordinated oxygen atoms, the coordinated oxygen atoms can form a multi-ring chelate with iron ions, and the chelating constant reaches more than 30, so that the chelating agent has strong chelating ability on the iron ions; and the chelating agent containing the aminomethylene diphosphonic acid contains P-C-P bond, has stronger bond energy and stronger combination than P-O-P or C-O-P bond of inorganic polymeric phosphate, and has high-temperature heat stability; even if the chelating agent containing aminomethylene diphosphonic acid is used in a strongly acidic environment at ph=1, the chelating constant is maintained at 20 or more; therefore, when the hydrogen sulfide remover is used for removing hydrogen sulfide, the hydrogen sulfide remover is not easy to fall off even if the removal environment is acidic, and stable removal efficiency is maintained.
On the other hand, chelating agents containing aminomethylene diphosphonic acid ionize a large amount of hydrogen ions in water and form a large amount of coordinated oxygen atoms, coordinated oxygen atoms and a large amount of Fe 3+ Forming stable chelate, the nitrogen atom in the chelating agent containing aminomethylene diphosphonic acid can also be combined with Fe 3+ The stable chelate is formed, so the hydrogen sulfide removing agent of the invention contains a large amount of Fe which is an effective component for removing hydrogen sulfide 3+ The removal efficiency of the hydrogen sulfide is very high.
In yet another aspect, fe 3+ Can be regenerated by oxygen (i.e. Fe 2+ Can be oxidized into Fe by oxygen 3+ ) The hydrogen sulfide removal agent is reused.
Containing Fe 3+ The compound is preferably an iron salt, and more preferably at least one of the following: fe (Fe) 2 (SO 4 ) 3 、 FeCl 3 ·6H 2 O and Fe (NO) 3 ) 3 。
According to the hydrogen sulfide removing agent of the present invention, the chelating agent containing aminomethylene diphosphonic acid is a cross-linked product of aminomethylene diphosphonic acid and a base having an amino group at the end.
According to the hydrogen sulfide removing agent of the invention, the chelating agent contains aminomethylene diphosphonic acid (abbreviated as AMDPA in English), and because the chelating agent contains a large amount of AMDPA, the AMDPA forms a large amount of coordinated oxygen atoms after ionization in water, a large amount of Fe can be chelated 3+ Therefore, the key groups for removing the hydrogen sulfide are increased, and the efficiency for removing the hydrogen sulfide is improved.
In addition, due to the presence of amino groups in the structure of AMDPA, the chelating agent containing aminomethylene diphosphonic acid can be formed by crosslinking with a matrix comprising amino groups at the end by a crosslinking agent.
Among them, glutaraldehyde and glyoxal are preferable as the crosslinking agent.
According to the hydrogen sulfide removing agent of the present invention, the substrate having an amino group at the end is a conjugate of a hydroxyl group-containing substrate and an amino group-containing silane coupling agent.
The hydrogen sulfide removing agent according to the present invention, wherein the hydroxyl group-containing matrix and the amino group-containing silane coupling agent form a conjugate through a chemical bond of the hydroxyl group and the amino group, thereby providing a substrate for crosslinking the AMDPA.
According to the hydrogen sulfide removing agent, the substrate containing hydroxyl is mesoporous silica containing hydroxyl.
Mesoporous silica is selected because the mesoporous silica contains Si-O-Si bonds, and when the mesoporous silica is treated by an alkaline solution, the Si-O bonds can be formed after the chemical bonds are opened, so that conditions are provided for coupling an amino-containing silane coupling agent; in addition, because the specific surface area of the mesoporous silica is large, more Si-OH bonds can be formed, more silane coupling agents containing amino groups can be coupled, more AMDPA can be crosslinked, and more Fe is finally chelated 3+ 。
Mesoporous silica contains abundant mesopores, and forms a relatively closed internal microenvironment in the mesopores so as to enrich reactants in each step, thereby improving the reaction efficiency; and in a relatively closed internal environment, chelated Fe 3+ Is not easy to fall off, improves the removal of hydrogen sulfideStability of the agent.
According to another aspect of the present invention, there is provided a method for preparing a hydrogen sulfide remover, comprising the steps of: chelating agent containing aminomethylene diphosphonic acid and Fe containing 3+ The chelate compound is obtained as the hydrogen sulfide remover.
Preferably, chelating agents containing aminomethylene diphosphonic acid and Fe-containing 3+ The mass ratio of the compounds is 1:7.5-1:25.
Specifically, a chelating agent containing aminomethylene diphosphonic acid and Fe are generally used 3+ Dispersing the compound in the solution according to a certain proportion, carrying out chelation reaction for a period of time at a certain temperature, and carrying out suction filtration after the reaction is finished; and drying and roasting filter residues to obtain chelate serving as a hydrogen sulfide remover.
Chelating agent containing aminomethylene diphosphonic acid and Fe containing 3+ The mass ratio of the compounds of (3) is preferably 1:7.5 to 1:25, particularly preferably 1:7.5, 1:8, 1:10, 1:12, 1:14, 1:15, 1:17, 1:20, 1:22 and 1:25.
Wherein, contains Fe 3+ The compound is preferably an iron salt, and more preferably at least one of the following: fe (Fe) 2 (SO 4 ) 3 、 FeCl 3 ·6H 2 O and Fe (NO) 3 ) 3 。
Wherein the certain temperature is 60-70deg.C, preferably 60deg.C, 63deg.C, 65deg.C, 68deg.C and 70deg.C.
Wherein, the certain time is 4-6 h, and particularly preferably 4h, 4.5h, 5h, 5.5h and 6h.
More specifically, the following equations show examples of chelating agents and iron chloride as cross-links between AMDPA and a substrate having an amino group at the end, and the following operation is performed.
Preparing an iron salt solution with the mass fraction of 25% -50%, and weighing and dispersing the chelating agent in the iron salt solution according to the proportion (converted into the mass ratio of 1:7.5-1:25) of the chelating agent to the volume ratio of 1:30-50 (g/mL) of the iron salt solution; then heating to 60-70 ℃ and chelating for 4-6 h; after the reaction is finished, vacuum suction filtration is carried out, and filter residues and filtrate are respectively collected; the collected filtrate is a reclaimed ferric salt solution and can be reused; and (3) sending the collected filter residues into a baking oven, drying the filter residues to constant weight at 50-60 ℃, taking out the filter residues, then putting the filter residues into a muffle furnace, roasting the filter residues for 4-5 hours at 300-400 ℃, taking out the filter residues, cooling the filter residues to room temperature, and then preserving the filter residues in a glass drier to obtain the chelate serving as the hydrogen sulfide remover.
An exemplary reaction equation for this step is shown below.
The preparation method comprises the preparation steps of chelating agent containing aminomethylene diphosphonic acid:
the AMDPA is crosslinked with a matrix with the tail end comprising amino groups through a crosslinking agent to obtain a chelating agent containing amino methylene diphosphonic acid;
preferably, the mass-volume ratio of the matrix with the tail end comprising the amino group and the AMDPA is 1:40-1:60 g/ml;
preferably, the pore-forming agent is added during the preparation of the chelating agent comprising aminomethylene bisphosphonic acid.
Specifically, a substrate with an amino group at the tail end and AMDPA are crosslinked by a crosslinking agent according to a certain proportion, so as to obtain the chelating agent containing the amino methylene diphosphonic acid.
The mass to volume ratio of the substrate including the amino group at the end and the AMDPA is preferably 1:40 to 1:60g/ml, particularly preferably 1:40, 1:45, 1:50, 1:55 and 1:60g/ml.
Preferably, in the preparation of the chelating agent comprising aminomethylene diphosphonic acid, the pore-forming agent is preferably nano calcium carbonate, polystyrene and polyacrylate.
The mass ratio of the crosslinking agent to the matrix having amino groups at the end is 0.05:1 to 0.15:1, particularly preferably 0.05:1, 0.08:1, 0.1:1, 0.13:1 and 0.15:1.
The reaction temperature is preferably 60 to 70℃and particularly preferably 60℃63℃65℃68℃and 70 ℃.
The reaction time is preferably from 4 to 6 hours, particularly preferably 4 hours, 4.5 hours, 5 hours, 5.5 hours and 6 hours.
Taking the reaction of a substrate having an amino group at the end and AMDPA as an example in the following equation, the specific procedure is as follows:
firstly, mixing nano calcium carbonate into AMDPA according to the mass ratio of 1:0.1-0.2 (g/g) of AMDPA to nano calcium carbonate, and fully mixing; dispersing the matrix with the amino at the tail end into the AMDPA solution according to the proportion of the mass of the matrix with the amino at the tail end to the volume ratio of the AMDPA solution of 1:40-60 (g/mL), and fully mixing; preparing glutaraldehyde solution with the mass fraction of 5%, adding glutaraldehyde solution as a cross-linking agent according to the proportion of the mass of a matrix with amino groups at the tail end and the volume ratio of glutaraldehyde solution of 1:1-3 (g/mL), heating to 70-80 ℃ by using a plurality of thermostat water baths, reacting for 6-8 h, performing vacuum filtration after the reaction is finished, repeatedly washing by using dilute hydrochloric acid until no liquid drops flow out, and respectively collecting filter residues and filtrate, wherein the filtrate is unreacted AMDPA solution and can be reused; and (3) putting the filter residues into a baking oven, drying the filter residues to constant weight at the temperature of 50-60 ℃, and then storing the filter residues in a glass drier to obtain the chelating agent containing the aminomethylene diphosphonic acid.
An exemplary substrate and AMDPA reaction equation for the end comprising an amino group for this step is as follows:
the preparation method according to the invention comprises the preparation steps of a matrix comprising an amino group at the end:
and coupling the hydroxyl-containing matrix with an amino-containing silane coupling agent to obtain a matrix with an amino group at the tail end.
Preferably, the mass ratio of the hydroxyl-containing matrix to the amino-containing silane coupling agent is 1:1-1:5.
Specifically, the amino group-containing silane coupling agent is preferably at least one of the following: KH-540 (gamma-aminopropyl trimethoxysilane), KH-550 (gamma-aminopropyl triethoxysilane) and KH-620 (N-beta-aminoethyl-gamma-aminopropyl methyldimethoxysilane).
More specifically, the following reaction equation showing a hydroxyl group-containing substrate and an amino group-containing silane coupling agent is exemplified, and the specific operation is: weighing the hydroxyl-containing matrix and the silane coupling agent according to the mass ratio of the hydroxyl-containing matrix to the silane coupling agent of 1:1-5 (g/g), dispersing the hydroxyl-containing matrix and the silane coupling agent in 95% (v/v) ethanol according to the volume ratio of 95% (v/v) ethanol of 1:100-300 (g/mL), heating to 90-100 ℃ by using a digital display constant temperature water bath kettle, condensing and refluxing for 4-6 hours, taking out, vacuum filtering, and respectively collecting filter residues and filtrate; the collected filtrate is used for recovering ethanol; and (3) sending the collected filter residues into a baking oven, drying the filter residues to constant weight at the temperature of 40-60 ℃, and then storing the filter residues in a glass drier to obtain a matrix with the hydroxyl at the tail end.
An exemplary reaction equation for this step is as follows, wherein the amino-containing silane coupling agent is KH-550 (gamma-aminopropyl triethoxysilane).
The preparation method comprises the steps of preparing a matrix containing hydroxyl groups:
the substrate is treated by alkaline solution to obtain a substrate containing hydroxyl; the matrix is preferably mesoporous silica.
Wherein the alkaline solution is selected from at least one of the following solutions: sodium hydroxide, lithium hydroxide, potassium hydroxide, and calcium hydroxide.
Preferably, the alkaline solution is a sodium hydroxide solution, preferably 25% to 50% by mass, particularly preferably 25%, 30%, 35%, 40%, 45% and 50% by mass.
Specifically, the following reaction equation is taken as an example, and the specific operation is: firstly preparing a sodium hydroxide solution with the mass fraction of 25-50%, weighing mesoporous silica, dispersing the mesoporous silica in the sodium hydroxide solution according to the volume ratio of the mesoporous silica to the sodium hydroxide solution of 1:10-30 (g/mL), heating the solution to 80-100 ℃ by a digital display constant temperature water bath, taking out the solution after treatment for 3-6 hours, washing the solution until the solution is neutral by purified water, combining the washing solution with the pretreated waste solution, carrying out neutralization treatment, discharging the solution after reaching the standard, putting the washed mesoporous silica in an oven, drying the dried solution to constant weight at 40-60 ℃, and storing the dried solution in a glass dryer to prepare the hydroxyl-containing matrix.
The mechanism of treatment with mesoporous silica and sodium hydroxide solution in the preparation method of the present invention is as follows.
According to another aspect of the present invention, there is provided a method for removing hydrogen sulfide, using the hydrogen sulfide remover of the present invention as a remover for removing hydrogen sulfide by a dry method.
The hydrogen sulfide removal by the hydrogen sulfide removal agent of the present invention is exemplified by a laboratory dry process.
Taking 0.5-1.0 g of the hydrogen sulfide removing agent, placing the hydrogen sulfide removing agent into a U-shaped bubbling pipe with the inner diameter of 4mm, placing the U-shaped bubbling pipe into a digital display constant-temperature water bath kettle for constant temperature, and when the temperature of the U-shaped bubbling pipe reaches 40-50 ℃, using the hydrogen sulfide containing agent with the concentration of 200mg/m 3 The raw material gas of (2) enters a U-shaped bubbling pipe to react with a hydrogen sulfide removing agent at the flow rate of 50mL/min under normal pressure, oxygen is introduced to regenerate the desulphurized hydrogen sulfide removing agent, the flow rate of the oxygen is 200mL/min, the concentration of the outlet hydrogen sulfide is detected by adopting an LC-2 type hydrogen sulfide detector, and when the concentration of the outlet hydrogen sulfide reaches 6mg/m 3 At this point, aeration was stopped, at which point the hydrogen sulfide removal agent was considered to penetrate, and the penetrating sulfur capacity was calculated.
The mechanism of removing hydrogen sulfide by using the hydrogen sulfide remover of the present invention is as follows.
The oxygen is introduced mainly for regenerating the hydrogen sulfide removing agent, and can be recycled. The regeneration principle is 4Fe 2+ +O 2 +4H + ＝4Fe 3+ +2H 2 O。
The hydrogen sulfide removing agent has high and stable hydrogen sulfide removing efficiency.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not limiting to the scope of the claims.
Wherein, examples 1 to 3 are the preparation method of the hydrogen sulfide remover; examples 4 to 6 are methods for dry removal of hydrogen sulfide using the hydrogen sulfide removal agents prepared in examples 1 to 3. Comparative example 1 is a process for removal of hydrogen sulfide using the prior art.
Example 1
Firstly, preparing mesoporous silica containing hydroxyl, wherein the specific operation of the step S1 is as follows:
firstly preparing a sodium hydroxide solution with the mass fraction of 25%, weighing mesoporous silica to be dispersed in the sodium hydroxide solution according to the mass ratio of the mesoporous silica to the sodium hydroxide solution of 1:10 (g/mL), heating to 80 ℃ by a digital display constant-temperature water bath, treating for 3 hours, taking out, washing with purified water until the solution is neutral, combining washing solution with pretreated waste liquid, neutralizing, discharging after reaching standards, putting the washed mesoporous silica into a baking oven, drying to constant weight at 40 ℃, and storing in a glass drier to prepare the hydroxyl-containing matrix.
Then, a step S2 of preparing a substrate with an amino group at the end, wherein the specific operation of the step is as follows:
weighing the hydroxyl-containing matrix and the silane coupling agent according to the mass ratio of the hydroxyl-containing matrix to the silane coupling agent of 1:1 (g/g), dispersing the hydroxyl-containing matrix and the silane coupling agent in 95% (v/v) ethanol according to the volume ratio of 95% (v/v) ethanol of 1:100 (g/mL), heating to 90-DEG C by a digital display constant temperature water bath kettle, condensing and refluxing for 4 hours, taking out, performing vacuum suction filtration, and respectively collecting filter residues and filtrate; the collected filtrate is used for recovering ethanol; and (3) sending the collected filter residues into a baking oven, drying the filter residues to constant weight at the temperature of 40 ℃, and then storing the filter residues in a glass drier to obtain a matrix containing amino, wherein the amino silane coupling agent is gamma-aminopropyl triethoxy silane.
Then, step S3 is performed: the chelant containing aminomethylene diphosphonic acid is prepared, and the specific operation of the steps is as follows:
firstly, mixing nano calcium carbonate into AMDPA according to the mass ratio of AMDPA to nano calcium carbonate of 1:0.1 (g/g), and fully mixing; dispersing the matrix with the amino at the tail end into the AMDPA solution according to the proportion of the mass of the matrix with the amino at the tail end to the volume ratio of the AMDPA solution of 1:40 (g/mL), and fully mixing; preparing glutaraldehyde solution with the mass fraction of 5%, adding glutaraldehyde solution as a cross-linking agent according to the proportion of the mass of a matrix with amino groups at the tail end to the glutaraldehyde solution volume ratio of 1:1 (g/mL), heating to 70 ℃ by using a plurality of thermostat water baths, reacting for 6 hours, performing vacuum filtration after the reaction is finished, repeatedly washing by using dilute hydrochloric acid until no liquid drops flow out, and respectively collecting filter residues and filtrate, wherein the filtrate is unreacted AMDPA solution and can be reused; and (3) putting the filter residues into a baking oven, drying the filter residues to constant weight at the temperature of 50 ℃, and storing the filter residues in a glass drier to obtain the chelating agent containing the aminomethylene diphosphonic acid.
Finally, step S4 is carried out: the preparation of the hydrogen sulfide removing agent comprises the following specific operations:
preparing an iron salt solution with the mass fraction of 25%, and weighing and dispersing the chelating agent in the iron salt solution according to the proportion (converted into the mass ratio of 1:7.5) of the mass of the chelating agent to the volume ratio of 1:30 (g/mL) of the iron salt solution; then heating to 60 ℃, and carrying out chelation reaction for 4 hours; after the reaction is finished, vacuum suction filtration is carried out, and filter residues and filtrate are respectively collected; the collected filtrate is a reclaimed ferric salt solution and can be reused; the collected filter residues are sent into a baking oven to be dried to constant weight at the temperature of 50 ℃, taken out, then put into a muffle furnace to be baked for 4 hours at the temperature of 300 ℃ and taken out, and after the temperature is reduced to room temperature, the filter residues are stored in a glass drier, and the chelate is prepared and obtained as a hydrogen sulfide removing agent, wherein the iron salt is FeCl 3 ·6H 2 O。
Example 2
Firstly, preparing mesoporous silica containing hydroxyl, wherein the specific operation of the step S1 is as follows:
firstly preparing a 40% sodium hydroxide solution, weighing mesoporous silica to be dispersed in the sodium hydroxide solution according to the mass ratio of the mesoporous silica to the sodium hydroxide solution of 1:20 (g/mL), heating to 90 ℃ by a digital display constant-temperature water bath, treating for 4 hours, taking out, washing with purified water until the solution is neutral, combining washing solution with pretreated waste liquid, neutralizing, discharging after reaching standards, putting the washed mesoporous silica into a baking oven, drying to constant weight at 50 ℃, and storing in a glass drier to prepare the mesoporous silica containing hydroxyl.
Then, a step S2 of preparing a substrate with an amino group at the end, wherein the specific operation of the step is as follows:
weighing the hydroxyl-containing matrix and the silane coupling agent according to the mass ratio of the hydroxyl-containing matrix to the silane coupling agent of 1:3 (g/g), dispersing the hydroxyl-containing matrix and the silane coupling agent in 95% (v/v) ethanol according to the volume ratio of 95% (v/v) ethanol of the hydroxyl-containing matrix to 1:200 (g/mL), heating to 95 ℃ by a digital display constant temperature water bath kettle, condensing and refluxing for 5 hours, taking out, performing vacuum suction filtration, and respectively collecting filter residues and filtrate; the collected filtrate is used for recovering ethanol; and (3) sending the collected filter residues into a baking oven, drying the filter residues to constant weight at 50 ℃, and then storing the filter residues in a glass drier to obtain a matrix with the tail end containing amino groups. Wherein the aminosilane coupling agent is gamma-aminopropyl trimethoxy silane.
Then, step S3 is performed: the chelant containing aminomethylene diphosphonic acid is prepared, and the specific operation of the steps is as follows:
firstly, mixing nano calcium carbonate into AMDPA according to the mass ratio of AMDPA to nano calcium carbonate of 1:0.15 (g/g), and fully mixing; dispersing the matrix with the amino at the tail end into the AMDPA solution according to the proportion of the mass of the matrix with the amino at the tail end to the volume ratio of 1:50 (g/mL), and fully mixing; preparing glutaraldehyde solution with the mass fraction of 5%, adding glutaraldehyde solution as a cross-linking agent according to the proportion of the mass of a matrix with amino groups at the tail end to the glutaraldehyde solution volume ratio of 1:2 (g/mL), heating to 75 ℃ by using a plurality of thermostat water baths, reacting for 7 hours, performing vacuum filtration after the reaction is finished, repeatedly washing by using dilute hydrochloric acid until no liquid drops flow out, and respectively collecting filter residues and filtrate, wherein the filtrate is unreacted AMDPA solution and can be reused; and (3) putting the filter residues into a baking oven, drying the filter residues to constant weight at the temperature of 55 ℃, and storing the filter residues in a glass drier to obtain the chelating agent containing the aminomethylene diphosphonic acid.
Finally, step S4 is carried out: the preparation of the hydrogen sulfide removing agent comprises the following specific operations:
preparing 30% ferric salt solution by mass fraction, and weighing and dispersing the chelating agent in the ferric salt solution according to the proportion (converted into the mass ratio of 1:12) of the chelating agent to the ferric salt solution by volume ratio of 1:40 (g/mL); then heating to 65 ℃ and carrying out chelation reaction for 5 hours; after the reaction is finished, vacuum suction filtration is carried out, and filter residues and filtrate are respectively collected; the collected filtrate is a reclaimed ferric salt solution and can be reused; and (3) sending the collected filter residues into a baking oven, drying the filter residues to constant weight at the temperature of 55 ℃, taking out the filter residues, then putting the filter residues into a muffle furnace, roasting the filter residues for 4.5 hours at the temperature of 350 ℃, taking out the filter residues, cooling the filter residues to room temperature, and storing the cooled filter residues in a glass dryer to obtain the chelate serving as the hydrogen sulfide remover.
Example 3
Step S1 is first performed: the preparation method comprises the following specific steps of:
firstly preparing 50% sodium hydroxide solution, weighing mesoporous silica, dispersing the mesoporous silica in the sodium hydroxide solution according to the mass-to-volume ratio of the mesoporous silica to the sodium hydroxide solution of 1:30 (g/mL), heating the solution to 100 ℃ by a digital display constant-temperature water bath, taking out the solution after treatment for 6 hours, washing the solution to be neutral by purified water, combining the washing solution with the pretreated waste liquid, carrying out neutralization treatment, discharging the solution after reaching standards, putting the washed mesoporous silica into a baking oven, drying the solution to constant weight at 60 ℃, and storing the dried solution in a glass drier to prepare the hydroxyl-containing matrix.
Then, a step S2 of preparing a substrate with an amino group at the end, wherein the specific operation of the step is as follows:
the following reaction equation showing a hydroxyl group-containing substrate and an amino group-containing silane coupling agent is exemplified, and the specific operation is as follows: weighing the hydroxyl-containing matrix and the silane coupling agent according to the mass ratio of the hydroxyl-containing matrix to the silane coupling agent of 1:5 (g/g), dispersing the hydroxyl-containing matrix and the silane coupling agent in 95% (v/v) ethanol according to the volume ratio of 95% (v/v) ethanol of the hydroxyl-containing matrix to the silane coupling agent of 1:300 (g/mL), heating to 100 ℃ by a digital display constant temperature water bath kettle, condensing and refluxing to treat 6h, taking out, performing vacuum suction filtration, and collecting filter residues and filtrate respectively; the collected filtrate is used for recovering ethanol; and (3) sending the collected filter residues into a baking oven, drying the filter residues to constant weight at the temperature of 60 ℃, and then storing the filter residues in a glass drier to obtain the amino-containing matrix. Wherein the aminosilane coupling agent is 3-aminopropyl trimethoxy silane.
Then, step S3 is performed: the chelant containing aminomethylene diphosphonic acid is prepared, and the specific operation of the steps is as follows:
firstly, mixing nano calcium carbonate into AMDPA according to the mass ratio of AMDPA to nano calcium carbonate of 1:0.2 (g/g), and fully mixing; dispersing the matrix with the amino at the tail end into the AMDPA solution according to the proportion of the mass of the matrix with the amino at the tail end to the volume ratio of 1:60 (g/mL), and fully mixing; preparing glutaraldehyde solution with the mass fraction of 5%, adding glutaraldehyde solution as a cross-linking agent according to the proportion of the mass of a matrix with amino groups at the tail end to the glutaraldehyde solution volume ratio of 1:3 (g/mL), heating to 80 ℃ by using a plurality of thermostat water baths, reacting for 8 hours, performing vacuum filtration after the reaction is finished, repeatedly washing by using dilute hydrochloric acid until no liquid drops flow out, and respectively collecting filter residues and filtrate, wherein the filtrate is unreacted AMDPA solution and can be reused; and (3) putting the filter residues into a baking oven, drying the filter residues to constant weight at the temperature of 60 ℃, and storing the filter residues in a glass drier to obtain the chelating agent containing the aminomethylene diphosphonic acid.
Finally, step S4 is carried out: the preparation of the hydrogen sulfide removing agent comprises the following specific operations:
preparing 50% ferric salt solution by mass fraction, and weighing and dispersing the chelating agent in the ferric salt solution according to the proportion (converted into the mass ratio of 1:25) of the chelating agent to the ferric salt solution by volume ratio of 1:50 (g/mL); then heating to 70 ℃, and carrying out chelation reaction for 6 hours; after the reaction is finished, vacuum suction filtration is carried out, and filter residues and filtrate are respectively collected; the collected filtrate is a reclaimed ferric salt solution and can be reused; and (3) sending the collected filter residues into a baking oven, drying the filter residues to constant weight at the temperature of 60 ℃, taking out the filter residues, putting the filter residues into a muffle furnace, roasting the filter residues for 5 hours at the temperature of 400 ℃, taking out the filter residues, cooling the filter residues to room temperature, and storing the cooled filter residues in a glass dryer to obtain the chelate serving as the hydrogen sulfide removing agent.
Example 4
Taking 0.8g of the hydrogen sulfide removing agent prepared in the example 1, placing the hydrogen sulfide removing agent into a U-shaped bubbling pipe with the inner diameter of 4mm, placing the U-shaped bubbling pipe into a digital display constant-temperature water bath kettle for constant temperature, and when the temperature of the U-shaped bubbling pipe reaches 45 ℃, using the hydrogen sulfide containing agent with the concentration of 200mg/m 3 The raw material gas of (2) enters a U-shaped bubbling pipe to react with a hydrogen sulfide removing agent at the flow rate of 50mL/min under normal pressure, oxygen is introduced to regenerate the desulphurized hydrogen sulfide removing agent, the flow rate of the oxygen is 200mL/min, the concentration of the outlet hydrogen sulfide is detected by adopting an LC-2 type hydrogen sulfide detector, and when the concentration of the outlet hydrogen sulfide reaches 6mg/m 3 At this point, aeration was stopped, at which point the hydrogen sulfide removal agent was considered to penetrate, and the penetrating sulfur capacity was calculated.
Example 5
In this example, the hydrogen sulfide removal agent prepared in example 2 was used to remove hydrogen sulfide, and the other conditions were the same as in example 4.
Example 6
The hydrogen sulfide removal agent prepared in example 3 was used in example 6 to remove hydrogen sulfide, with the other conditions being the same as in example 4.
Comparative example 1
In comparative example 1, a composite of carbon nanotubes and hydrous iron oxide disclosed in CN112717931a was used as a hydrogen sulfide removing agent, and the other conditions were the same as in example 4.
Applicants tested the breakthrough sulfur capacities of examples 4-6 and comparative example 1.
The detection method and calculation method of the penetrating sulfur capacities of examples 4 to 6 and comparative example 1 are as follows:
the breakthrough sulfur capacity is calculated as the mass fraction of sulfur in the hydrogen sulfide removal agent, the values are expressed in%, calculated as follows:wherein C represents the mass concentration (kg/m) of sulfur in the feed gas 3 )；V 1 ，V 2 A value (mL) representing the gas volume at the start and stop of the wet gas flow meter; m represents the mass (kg) of the hydrogen sulfide removing agent in the reactor.
The sulfur capacity detection conditions of examples 4 to 6 and comparative examples 1 and 2 were: the temperature is 40 ℃, the pressure is normal pressure (usually 1 atmosphere), and the penetration concentration is 6mg/m 3 ；
The detection steps are as follows:
taking 0.8g of hydrogen sulfide removing agent, placing into a U-shaped bubbling pipe, and keeping the temperature in a water bath kettle, when the temperature of the U-shaped bubbling pipe reaches 45 ℃, using a catalyst containing 200mg/m of hydrogen sulfide 3 The raw material gas of (2) enters a U-shaped bubbling pipe to react with a hydrogen sulfide removing agent at the flow rate of 50mL/min under normal pressure, oxygen is introduced to regenerate the desulphurized hydrogen sulfide removing agent, the flow rate of the oxygen is 200mL/min, the concentration of the outlet hydrogen sulfide is detected by adopting an LC-2 type hydrogen sulfide detector, and when the concentration of the outlet hydrogen sulfide reaches 6mg/m 3 Stopping ventilation when the hydrogen sulfide remover penetrates; the values of the gas volumes at start and stop with a wet gas flow meter.
The calculation was performed according to the above formula, and the detection data were obtained as shown in table 1.
TABLE 1
As can be seen by comparing example 4 with comparative example 1, the hydrogen sulfide remover prepared in example 1 was used because of the chelating agent containing aminomethylene diphosphonic acid and Fe 3+ Has strong chelating force, fe 3+ Is not easy to fall off and is due to chelationRich Fe 3+ More hydrogen sulfide was removed, so that penetrating sulfur Rong Yuan of example 4 was higher than that of comparative example 1, and it was found that the efficiency of removing hydrogen sulfide using the hydrogen sulfide remover of the present invention was high.
While examples 4 to 6 using the hydrogen sulfide removal agent of the present invention all maintained high and slightly different penetrating sulfur capacities, also demonstrated that the hydrogen sulfide removal efficiency was high and stable using the hydrogen sulfide removal agent of the present invention.
It will be apparent to those skilled in the art that various modifications and variations can be made to the embodiments of the present invention without departing from the spirit and scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (7)
1. The hydrogen sulfide remover is characterized by being prepared by the following steps:
(1) The mesoporous silica is treated by alkaline solution to obtain a matrix containing hydroxyl;
(2) Coupling a hydroxyl-containing matrix with an amino-containing silane coupling agent to obtain a matrix with an amino group at the tail end;
(3) The substrate with the tail end comprising amino is crosslinked with amino methylene diphosphonic acid through a crosslinking agent to obtain a chelating agent containing amino methylene diphosphonic acid, wherein the crosslinking agent is glutaraldehyde;
(4) Chelating agent containing aminomethylene diphosphonic acid and chelating agent containing the sameThe chelate is obtained by chelating the compound of (2) to obtain the chelate, namely the hydrogen sulfide remover.
2. The hydrogen sulfide removal agent of claim 1, wherein the alkaline solution is selected from at least one of the following: sodium hydroxide, lithium hydroxide, potassium hydroxide, and calcium hydroxide.
3. The hydrogen sulfide removal agent according to claim 1, wherein the amino group-containing silane coupling agent is selected from at least one of: gamma-aminopropyl trimethoxysilane, gamma-aminopropyl triethoxysilane, N-beta-aminoethyl-gamma-aminopropyl methyldimethoxysilane.
4. The hydrogen sulfide removal agent according to claim 1, wherein the mass ratio of the hydroxyl group-containing matrix to the amino group-containing silane coupling agent is 1:1 to 1:5.
5. The hydrogen sulfide remover according to claim 1, wherein the mass-to-volume ratio of the substrate including the amino group at the end to the aminomethylene diphosphonic acid is 1:40g/ml to 1:60g/ml.
6. The hydrogen sulfide removal agent according to claim 1, wherein the chelating agent containing aminomethylene diphosphonic acid and the catalyst containingThe mass ratio of the compounds is 1:7.5-1:25.
7. The hydrogen sulfide removal agent as claimed in claim 1, wherein said catalyst comprisesIs selected from at least one of the following: />、/>。
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